Modified particles, carrier prepared therefrom, olefin polymerization catalyst component prepared therefrom, olefin polymerization catalyst prepared therefrom, and process for preparing olefin polymer

ABSTRACT

Modified particles obtained by contacting dry particles(a) with an organometallic compound(b), and subsequently a compound(c) having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group and an electron attractive group; a carrier comprising said particles; a catalyst component for olefin polymerization comprising said particles; a catalyst for olefin polymerization comprising said particles(A) and a transition metal compound(B), or an additional organometallic compound (C) therewith; and a method for producing an olefin polymer with said catalyst for olefin polymerization. According to the present invention, there is provided a catalyst for polymerizing an olefin giving an olefin polymer excellent in particle properties with a high activity when applied to a slurry polymerization or gas phase polymerization, and a method for producing a olefin polymer using said catalyst.

This application is the national phase under 35 U.S.C. §371 of PCTInternational Application No. PCT/JP98/03680 which has an Internationalfiling date of Aug. 20, 1998 which designated the United States ofAmerica.

TECHNICAL FIELD

The present invention relates to particles which are useful as a carrierand a catalyst component for olefin polymerization a catalyst for olefinpolymerization using the same, and method for producing an olefinpolymer using said catalyst for olefin polymerization.

BACKGROUND ARTS

A lot of reports on a method for producing an olefin polymer using atransition metal compound have already been made. As the example ofusing a metallocene transition metal compound, for example, JapanesePatent Publication (Kokai) No.58-19309 discloses a method of producingan olefin polymer using bis(cyclopentadienyl)zirconium dichloride andmethylaluminoxane. Japanese Patent Publication(kohyo) No.1-502036discloses a method of producing an olefin polymer usingbis(pentamethylcyclopentadienyl)zirconium dimethyl and n-butylammoniumtetrakisphenylborate. Japanese Patent Publication(Kokai) No.5-178923discloses a method of producing an olefin polymer usingdimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dimethyl,dimethylanilinumtetrakis(pentafluorophenyl)borate and triethylaluminum.Furthermore, a lot of examples using a non-metallocene transition metalcompound are disclosed in J. Amer. Chem. Soc., 115, 8493(1993), PlasticsEngineering, March. 77(1996), WO96/23010 and the like.

Since catalysts using these transition metal compounds are soluble in areaction system, when used in the polymerization accompanying formationof polymer particles (e.g. slurry polymerization, gas phasepolymerization, etc.), the shape of the formed polymer is irregular tocause formation of large polymer particles, an agglomerate polymer andfine polymer particles, decrease in bulk density of the polymer,adhesion of the polymer to the polymerization reactor wall.Consequently, poor heat transfer and poor cooling in the reactor, andthe like are caused, which results in difficulty in stable operation andlowering of the productivity.

In order to apply the transition metal compound to the polymerizationaccompanying formation of polymer particles (e.g. slurry polymerization,gas phase polymerization), it is necessary that not only sufficientpolymerization activity is exerted but also the polymer excellent inshape and particle properties is obtained. To solve these problems, amethod of supporting a transition metal compound on a carrier has beenproposed.

As one method, for example, a method of fixing or supporting all or apart of a catalyst component such as metallocene complex,methylaluminoxane or the like on an inorganic metal oxide carrier suchas silica or the like has been reported.

For example, Japanese Patent Publication(Unexamined) Nos. 60-35006,60-35007 and 60-35008 respectively disclose a method ofdepositing/adhering a soluble metallocene on a typical support (e.g.silica, alumina, polyethylene, etc.) to convert into a supportedheterogeneous catalyst and using a combination of the catalyst andaluminoxane in the slurry polymerization or gas phase polymerization.

Japanese Patent Publication (Unexamined) No. 61-108610 discloses amethod of producing a polyolefin polymer using a solid catalystcomponent obtained by adding a calcined silica tobis(cyclopentadienyl)zirconium dichloride and a reaction product oftrimethylaluminum and water.

Japanese Patent Publication(Unexamined) No. 61-276805 discloses a methodof producing an olefin polymer using an inorganic oxide-containingorganoaluminum component, obtained by reacting a mixture ofmethylaluminoxane and trimethylaluminum with silica, andbis(cyclopentadienyl)zirconium dichloride.

Japanese Patent Publication(Unexamined) No. 61-296008 discloses a methodof producing an olefin polymer using a solid catalyst containingaluminum and zirconium, obtained by treating silica in turn withmethylaluminoxane and bis(cyclopentadienyl)zirconium chloride.

As the improved method, for example, there have been reported a methodof using a solid catalyst component obtained by fixing/supporting all ora part of a catalyst component such as metallocene complex,methylaluminoxane, etc. on an in organic metal oxide carrier such assilica, etc., and aluminoxane or organoaluminum, and a method of using apre-polymerized catalyst obtained by carrying out prepolymerization.Japanese Patent Publication (Kokai) No.63-51407 discloses a method ofproducing an olefin polymer using a solid catalyst component obtained bytreating silica in turn with methylaluminoxane andbis(cyclopentadienyl)zirconium dichloride, and methylaluminoxane.

Japanese Patent Publication (Kokai) No.63-89505 discloses a method ofproducing an olefin polymer using a solid catalyst component obtained bytreating silica in turn with methylaluminoxane andbis(cyclopentadienyl)zirconium dichloride, and triisobutylaluminum or amethod of producing an olefin polymer using a solid catalyst componentpre-polymerized with the solid catalyst component andtriisobutylaluminum.

In the above prior arts, use of aluminoxane is essential. Thisaluminoxane must be separately synthesized and a lot of steps arerequired and are complicated. The aluminoxane is unstable and costly.Regarding the solid catalyst component obtained by combining thealuminoxane with an inorganic metal oxide carrier such as silica, theamount of aluminum used is large and activity per 1 mol of an Al atomwas low. To solve these problems, there has been reported a method ofproducing an olefin polymer using a solid catalyst component obtained byreacting an organoaluminum with water in the presence of an inorganicmetal oxide carrier such as silica to form aluminoxane.

For example, Japanese Patent Publication (Kokai) No.61-31404 discloses amethod of producing an olefin polymer using a catalyst obtained byadding water, trimethylaluminum and bis(cyclopentadienyl)zirconiumdichloride in turn to silica.

Japanese Patent Publication (Kokai) No. 1-1207303 discloses a method ofproducing an olefin polymer using silica gel powders containing asupported metallocene-methylaluminoxane catalyst complex, obtained byadding silica gel not dehydrated, containing water to trimethylaluminumand treating the resultant with bis(n-butylcyclopentadienyl)zirconiumdichloride.

Japanese Patent Publication (Kokai) No. 3-234710 discloses a method ofproducing an olefin polymer using a prepolymerized solid catalyst,obtained by adding water, trimethylaluminum andbis(methylcyclopentadienyl)zirconium dichloride in turn to silica andfurther adding ethylene to the mixture, and triisobutylaluminum.

According to these prior arts, synthesis of aluminoxane and fixing ofthe component to an inorganic metal oxide carrier such as silica or thelike can be easily and simply performed. However, these methods requirecontrol of the amount of water used and it is difficult. Furthermore,the aluminoxane synthesized by this method and the solid catalystcomponent obtained by fixing the aluminoxane synthesized by this methodhave low activity, unlike separately synthesized aluminoxane and a solidcatalyst component obtained by fixing the separately synthesizedaluminoxane, and the particle properties of the resulting polymer arenot preferred.

There has been reported a method of producing an olefin polymer using asolid catalyst component obtained from a metallocene transition metalcompound, a boron compound and a carrier, or a solid catalyst componentobtained from a metallocene transition metal compound, a boron compound,an organoaluminum compound and a carrier.

For example, Japanese Patent Publication (Kohyo) No.5-502906 discloses amethod of producing an olefin polymer using a supported catalystobtained by adding a reaction product of bis(cyclopentadienyl)zirconiumdimethyl and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate tobasic alumina.

Japanese Patent Publication (Kokai) No. 6-336502 discloses a method ofproducing an olefin polymer using a solid catalyst component, obtainedfrom a carrier prepared by treating silica with triethylaluminum,ethylenebisindenyl zirconium dichloride andN,N-dimethylanilinumtetrakis(pentafluorophenyl)borate, and further,triisobutylaluminum.

However, the boron compound used in these prior arts must be separatelysynthesized and a lot of steps are required and are complicated. Sincethe amount of the boron compound to be incorporated into a carrier suchas silica is usually small and the reaction product of the metallocenetransition metal compound and boron compound is generally unstable, theactivity in case of polymerizing an olefin using the resulting solidcatalyst component was low.

There have recently been reported a method of producing a catalyst forolefin polymerization using an aluminum compound wherein a special groupis introduced, in place of aluminoxane and a boron compound, and atransition metal compound, or using them in combination with anorganoaluminum compound, and a method of producing an olefin polymerusing the same.

For example, Japanese Patent Publication(Unexamined) No. 6-329713discloses a method of producing an olefin polymer using a solidcomponent of an aluminum compound having an electron attractive group,obtained by reacting trimethylaluminum and pentafluorophenol, andbis(cyclopentadienyl)titanium dichloride. There is also described amethod of producing a catalyst component by supporting an aluminumcompound, wherein a special group is introduced, on an inorganic carrieror organic carrier. However, there is not disclosed the example ofactually supporting the aluminum compound having an electron attractivegroup obtained by reacting trimethylaluminum with pentafluorophenol, andthe polymerization activity in case of using a supported solid catalystcomponent as described in the publication was low.

Furthermore, there has recently been reported a catalyst for olefinpolymerization, composed of a modified clay, obtained by treating a claymineral with a compound capable of introducing a cation into layers, asa substitute of aluminoxane and a boron compound, a metallocene complexand an organoaluminum compound.

For example, Japanese Patent Publication (Kokai) No.7-224106 discloses amethod of producing an olefin polymer using a modified clay obtained byusing ferrocene, concentrated sulfuric acid and synthetic high puritymontmorillonite, triisobutylaluminum and ethylenebis(indenyl)zirconiumdichloride.

However, many clay minerals have irregular shape, particle diameter andparticle properties and, moreover, olefin polymers obtained by using theclay minerals, contain a large amount of irregular matters in shape andparticle properties. There is described that the modified clay isprepared in an aqueous solution to introduce a cation into layers of theclay mineral, however, water is essentially an inhibitor for olefinpolymerization and complete removal of water from the modified clay wasrequired but was difficult.

DISCLOSURE OF THE INVENTION

Under these circumstances, problems to be solved by the presentinvention, that is, an object of the present invention is to provideparticles capable of giving a polymer having excellent shape andparticle properties with high activity when a catalyst for olefinpolymerization obtained by using a transition metal compound is appliedto the polymerization accompanying formation of polymer particles (e.g.slurry polymerization, gas phase polymerization, etc.) by using incombination with the transition metal compound, a carrier consisting ofsaid particles, a catalyst component for olefin polymerizationconsisting of said particles, a catalyst for olefin polymerizationcomprising said particles, and a method for producing an olefin polymerby using said catalyst for olefin polymerization.

To accomplish the above object, the present inventors have intensivelyinvestigated about a method for producing an olefin polymer with atransition metal compound, particularly a method for producing an olefinpolymer according to the polymerization accompanying formation ofpolymer particles. As a result, the present inventors found modifiedparticles obtained by contacting dry particles with a specific compound,and accomplished the present invention.

The present invention relates to modified particles obtained bycontacting dry particles(a) with an organometallic compound(b), andsubsequently a compound(c) having a functional group containing anactive hydrogen or a non-proton donative Lewis basic functional group,and an electron attractive group.

Further, the present invention also relates to a carrier comprising saidparticles; a catalyst component for olefin polymerization, comprisingsaid particles; a catalyst for olefin polymerization, comprising saidparticles(A) and a transition metal compound(B), or an additionalorganometallic compound(C) therewith; and a method for producing anolefin polymer with said catalyst for olefin polymerization.

The present invention will be explained in detail below.

(a) Dry Particles

The modified particles of the present invention are obtained bycontacting dry particles(a) with an organometallic compound(b), andsubsequently a compound(c) having a functional group containing activehydrogen or a non-proton donative Lewis basic functional group and anelectron attractive group. The particles(a) used herein are dry andsubstantially contain no water, and substantially forms no aluminoxaneby contact with trialkylaluminum.

As the particles(a), there can be preferably used those which aregenerally used as a carrier. A porous substance having a uniformparticle diameter is preferred and an inorganic substance or an organicpolymer is preferably used.

Examples of the inorganic substance which can be used as theparticles(a) in the present invention include inorganic oxides andmagnesium compounds, and clays and clay minerals can also be used unlessno problem arises. These inorganic substances may be used incombination.

Specific examples of the inorganic oxide include SiO₂, Al₂O₃, MgO, ZrO₂,TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂ and mixtures thereof such as SiO₂—MgO,SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃, SiO₂—TiO₂—MgO, etc. Amongthese inorganic oxides, SiO₂ and/or Al₂O₃ are preferred. The aboveinorganic oxide may contain a small amount of carbonate, sulfate,nitrate and oxide components, such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃,Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O, Li₂O,etc.

Examples of the magnesium compound include magnesium halides such asmagnesium chloride, magnesium bromide, magnesium iodide, magnesiumfluoride and the like; alkoxymagnesium halides such as methoxymagnesiumchloride, ethoxymagnesium chloride, isopropoxymagnesium chloride,butoxymagnesium chloride, octoxymagnesium chloride and the like;aryloxymagnesium halides such as phenoxymagnesium chloride,methylphenoxymagnesium chloride and the like; alkoxymagnesiums such asethoxymagnesium, isopropoxymagnesium, butoxymagnesium,n-octoxymagnesium, 2-ethylhexoxymagnesium and the like;aryloxymagnesiums such as phenoxymagnesium, di-methylphenoxymagnesiumand the like; magnesium carboxylates such as magnesium laurate,magnesium stearate and the like.

Among them, magnesium halides or alkoxymagnesiums are preferred, andmagnesium chloride or butoxymagnesium is more preferred.

Examples of the clay or clay mineral include kaolin, bentonite, Kibushiclay, gaerome clay, allophane, hisingerite, pyrophylite, talc, a micagroup, a montmorillinite group, vermiculite, a chlorite group,palygorskite, kaolinite, nacrite, dickite, halloycite and the like.Among them, smectite, montmorillinite, hectorite, raponite and saponiteare preferred, and montmorillinite and hectorite are more preferred.

It is necessary that these inorganic substances are dried tosubstantially remove water, and those dried by a heat treatment arepreferred. The heat treatment is normally carried out at the temperatureof 100 to 1500° C., preferably 100 to 1000° C., and more preferably 200to 800° C. There can be used a method of passing the heated inorganicsubstance through a dried inert gas (e.g. nitrogen, argon) at a fixedflow rate for a few hours or more, or a method of evacuating for severalhours, but the method is not limited.

The average particle diameter of the inorganic substance is preferablyfrom 5 to 1000 μm, more preferably from 10 to 500 μm, and mostpreferably from 10 to 100 μm. The pore volume is preferably not lessthan 0.1 ml/g, and more preferably 0.3 to 10 ml/g. The specific surfacearea is preferably from 10 to 1000 m²/g, and more preferably from 100 to500 m²/g.

As the organic polymer used as the particles(a) in the presentinvention, any organic polymer may be used and a mixture of plural kindsof organic polymer may also be used. As the organic polymer, an organicpolymer having a functional group capable of reacting with theorganometallic compound(b) is preferred. Examples of the functionalgroup include functional group containing active hydrogen and anon-proton donative Lewis basic functional group. As the organic polymerwhich can be used as the particles(a), a polymer having a functionalgroup containing active hydrogen or a non-proton donative Lewis basicfunctional group is preferred.

The functional group containing active hydrogen may be any onecontaining an active hydrogen, and is not specifically limited. Specificexamples thereof include a primary amino group, secondary amino group,imino group, amide group, hydrazide group, amidino group, hydroxy group,hydroperoxy group, carboxyl group, formyl group, carbamoyl group,sulfonic acid group, sulfinic acid group, sulfenic acid group, thiolgroup, thioformyl group, pyrrolyl group, imidazolyl group, piperidylgroup, indazolyl group, carbazolyl group and the like. Among them, aprimary amino group, secondary amino group, imino group, amide group,hydroxy group, formyl group, carboxyl group, sulfonic acid group orthiol group is preferred. A primary amino group, secondary amino group,imino group, amide group or hydroxy group is particularly preferred.These groups may be substituted with a halogen atom or a hydrocarbongroup having 1 to 20 carbon atoms.

The non-proton donative Lewis basic functional group may be anyfunctional group having a Lewis basic portion containing no activehydrogen atom, and is not specifically limited. Specific examplesthereof include pyridyl group, N-substituted imidazolyl group,N-substituted indazolyl group, nitrile group, azido group, N-substitutedimino group, N,N-substituted amino group, N,N-substituted aminoxy group,N,N,N-substituted hydrazino group, nitroso group, nitro group, nitroxygroup, furyl group, carbonyl group, thiocarbonyl group, alkoxy group,alkyloxycarbonyl group, N,N-substituted carbamoyl group, thioalkoxygroup, substituted sulfinyl group, substituted sulfonyl group,substituted sulfonic acid group and the like. A heterocyclic group ispreferred, and an aromatic heterocyclic group having an oxygen atomand/or a nitrogen atom in the ring is more preferred. Among them,pyridyl group, N-substituted imidazolyl group and N-substituted indazoylgroups are particularly preferred and pyridyl group is most preferred.These groups may be substituted with a halogen atom or a hydrocarbongroup having 1 to 20 carbon atoms.

The amount of the functional group containing active hydrogen ornon-proton donative Lewis basic functional group is not specificallylimited, but is preferably from 0.01 to 50 mmol/g, and more preferablyfrom 0.1 to 20 mmol/g, in terms of a molar amount of the functionalgroup per g of the organic polymer.

The organic polymer having said functional group can be obtained, forexample, by polymerizing a monomer having a functional group containingactive hydrogen or a non-proton donative Lewis basic functional group,or this monomer and another monomer. At this time, it is preferred tocopolymerize the above monomers with a crosslinking polymerizablemonomer having two or more polymerizable unsaturated bonds.

Examples of the monomer having a functional group containing activehydrogen or a non-proton donative Lewis basic functional group includethe above monomer having a functional group containing active hydrogen,and a polymerizable unsaturated group or monomer having a functionalgroup having a Lewis basic portion containing no active hydrogen, and apolymerizable unsaturated group.

Examples of the polymerizable unsaturated group include alkenyl groupssuch as vinyl group, allyl group and the like; alkynyl groups such asethyne group and the like. Examples of the monomer having a functionalgroup containing active hydrogen and a polymerizable unsaturated groupinclude a vinyl group-containing primary amine, vinyl group-containingsecondary amine, vinyl group-containing amide compound and vinylgroup-containing hydroxy compound. Specific examples thereof includeN-(1-ethenyl)amine, N-(2-propenyl)amine, N-(1-ethenyl)-N-methylamine,N-(2-propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide,N-methyl-(1-ethenyl)amide, N-methyl-(2-propenyl)amide, vinyl alcohol,2-propen-1-ol, 3-buten-1-ol and the like.

Specific examples of the monomer having a functional group having aLewis basic portion containing no active hydrogen, and a polymerizableunsaturated group include vinylpyridine, vinyl(N-substituted)imidazoleand vinyl(N-substituted)indazole.

The other monomers having a polymerizable unsaturated group includeethylene, α-olefin and the like, and specific examples thereof includeethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, styrene andthe like. Among them, ethylene or styrene is preferred. Two or morekinds of these monomers may be used.

Specific examples of the crosslinking polymerizable monomer having twoor more polymerizable unsaturated groups include divinylbenzene and thelike.

The average particle diameter of the organic polymer is preferably from5 to 1000 μm, and more preferably from 10 to 500 μm. The pore volume ispreferably not less than 0.1 ml/g, and more preferably 0.3 to 10 ml/g.The specific surface area is preferably from 10 to 1000 m²/g, and morepreferably from 50 to 500 m²/g.

(b) Organometallic Compound

The organometallic compound (b) used in the present invention is anorganometallic compound represented by the following general formula(1):

R¹ _(n)AX_(q−n)  (1)

(wherein A represents a metal atom of the 2nd, 12th or 13th Group of thePeriodic Table of Element(IUPAC 1993); R¹ represents a hydrocarbon grouphaving 1 to 20 carbon atoms or a hydrocarbonoxy group having 1 to 20carbon atoms and a plurality of R¹ may be the same or different; Xrepresents a halogen atom or a hydrogen atom; n represents a numbersatisfying the expression 0<n≦q; and q is a valence number of the metalatom.).

A above preferably includes a boron atom, aluminum atom, magnesium atom,zinc atom and the like. When A is a boron atom or aluminum atom, thevalence number is 3 (q=3)m, and when A is magnesium atom or zinc atom,the valence number is 2(q=2). When A is a boron atom, R¹ is preferablythe hydrocarbon group described above, and specific examples of thereofinclude trialkylboranes such as trimethylborane, triethylborane,tripropylborane, tributylborane, triphenylborane and the like;dialkylhalidoboranes such as dimethylchloroborane, diethylchloroborane,dipropylchloroborane, dibutylchloroborane, diphenylchloroborane and thelike; dialkylhydrideborane such as dimethylhydridoborane,diethylhydridoborane, dipropyldihydridoborane, dibutylhydridoborane,diphenylhydridoborane and the like; alkyldihalideborane such asmethyldichloroborane, ethyldichloroborane, propyldichloroborane,butyldichloroborane, phenyldichloroborane and the like.

When A is an aluminum atom, R¹ is preferably the hydrocarbon groupdescribed above, and specific examples of thereof includetrialkylaluminums such as trimethylaluminum, triethylaluminum,tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-n-hexylaluminum and the like; dialkylaluminumhalides such as dimethylaluminum chloride, diethylaluminum halide,di-n-propylaluminum chloride, diisopropylaluminum chloride,di-n-butylaluminum chloride, diisobutylaluminum chloride,di-n-hexylaluminum chloride and the like; alkylaluminum dihalides suchas methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminumdichloride, isopropylaluminumdichloride, n-butylaluminumdichloride,isobutylaluminum dichloride, n-hexylaluminum dichloride and the like;dialkylaluminumhydrides such as dimethylaluminumhydride,diethylaluminumhydrido, di-n-propylaluminumhydride,diisopropylaluminumhydride, di-n-butylaluminumhydride,diisobutylaluminumhydride, di-n-hexylaluminumhydride and the like.

Trialkylaluminums are preferred, and trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-butylaluminum andtri-n-hexylaluminum are more preferred. Among them, trimethylaluminum,triethylaluminum and triisobutylaluminum are particularly preferred.

When A is a magnesium atom, R¹ is preferably the hydrocarbon groupdescribed above, and specific examples of thereof includediethylmagnesium, di-n-butylmagnesium and the like, and there is alsoincluded di-n-butoxymagnesium in which R¹ is the hydrocarbonoxy groupdescribed above. And, when A is a zinc atom, R¹ is preferably thehydrocarbon group described above, and specific examples of thereofinclude diethylzinc and the like.

The organometallic compound(b) is more preferably an organoaluminumcompound and organoboron compound, and an organoaluminum compound ismost preferred.

(c) Compound Having a Functional Group Containing Active Hydrogen or aNon-proton Donative Lewis Basic Functional Group, and an ElectronAttractive Group

The functional group containing active hydrogen or non-proton donativeLewis basic functional group of the compound(c) used in the presentinvention normally reacts with the organometallic compound.

The functional group containing active hydrogen and non-proton donativeLewis basic functional group are the same as those describedherein-above.

The compound(c) has an electron attractive group, but a substituentconstant σ of Hammett's rule can be used as an index of the electronattractive group. A functional group wherein the substituent constant σof Hammett's rule is positive corresponds to the electron attractivegroup.

Specific examples of the electron attractive group include a fluorineatom, chlorine atom, bromine atom, iodine atom, cyano group, nitrogroup, phenyl group, acetyl group, carbonyl group, thionyl group,sulfone group, carboxyl group and the like.

In the compound(c), a functional group containing active hydrogen and anon-proton donative Lewis basic functional group may be the same. And,the compound(c) may have plural kinds and/or a plurality of functionalgroups containing active hydrogen or non-proton donative Lewis basicfunctional groups, and electron attractive groups. Examples of thecompound(c) include amines, phosphines, alcohols, phenols, thiols,thiophenols, carboxylic acids and sulfonic acids, having an electronattractive group, and the like.

The compound (c) is preferably a compound represented by the followinggeneral formula (2):

R² _(m)ZH_(z−m)  General formula (2)

(wherein R² represents an electron attractive group or a groupcontaining an electron attractive group; Z represents an atom of the15th or 16th Group of the Periodic Table; H represents a hydrogen atom;and z represents a valence of Z, provided m is 1 when z is 2 and m is 1or 2 when z is 3).

Examples of the group containing an electron attractive group in R² ofthe general formula (2) include a halogenated alkyl group, halogenatedaryl group, cyanated aryl group, nitrated aryl group, ester group andthe like.

Specific examples of the halogenated alkyl group include fluoromethylgroup, chloromethyl group, bromomethyl group, iodomethyl group,difluoromethyl group, dichloromethyl group, dibromomethyl group,diiodomethyl group, trifluoromethyl group, trichloromethyl group,tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group,2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group,2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group,2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group,2,2,3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethylgroup, 2,2,2-trichloro-1-trichloromethylethyl group,2,2,2-tribromo-1-tribromomethylethyl group,2,2,2-triiodo-1-triiodomethylethyl group,1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group,1,1,3,3,3-hexachloro-2-trichloromethylpropylgroup,1,1,3,3,3-hexabromo-2-tribromomethylpropyl group,1,1,3,3,3-hexaiodo-2-triiodomethylpropyl group and the like.

Specific examples of the halogenated aryl group include 2-fluorophenylgroup, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group,3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group,3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group,3-iodophenyl group, 4-iodophenyl group, 2,6-difluorophenyl group,3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenylgroup, 2,6-dibromophenyl group, 3,5-dibromophenyl group,2,6-diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-trifluorophenylgroup, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group,2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenylgroup, pentabromophenyl group, pentaiodophenyl group,2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group,4-(trifluoromethyl)phenyl group, 2,6-di(trifluoromethyl)phenyl group,3,5-di(trifluoromethyl)phenyl group, 2,4,6-tri(trifluoromethyl)phenylgroup and the like.

Specific examples of the cyanated aryl group include 2-cyanophenylgroup, 3-cyanophenyl group, 4-cyanophenyl group and the like.

Specific examples of the nitrated aryl group include 2-nitrophenylgroup, 3-nitrophenyl group, 4-nitrophenyl group and the like.

Specific examples of the ester group include methoxycarbonyl group,ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonylgroup, phenoxycarbonyl group, trifluoromethyloxycarbonyl group,pentafluorophenyloxycarbonyl group and the like.

R² of the general formula (2) is preferably a halogenated alkyl orhalogenated aryl group, more preferably a fluoromethyl group,difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoromethylgroup, 2,2,3,3,3-pentafluoromethyl group,2,2,2-trifluoro-1-trifluoromethylethyl group,1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 4-fluorophenylgroup, 2,6-difluorophenyl group, 3,5-difluorophenyl group,2,4,6-trifluorophenyl group or pentafluorophenyl group, more preferablya trifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group,1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group orpentafluorophenyl group.

Z in the general formula (2) represents an atom of the 15th or 16thGroup of the Periodic Table, and H represents a hydrogen atom. Specificexamples of Z include a nitrogen atom, phosphorus atom, oxygen atom,sulfur atom and the like. Among them, a nitrogen atom or oxygen atom ispreferred and an oxygen atom is more preferred.

z represents a valence of Z. For example, z is 3 when Z is a nitrogenatom or a phosphorus atom, whereas, z is 2 when Z is am oxygen atom or asulfur atom. m is 1 when z is 2, whereas, m is 1 or 2 when z is 3.

Specific examples of the amines described as for the compound(c) includedi(fluoromethyl)amine, di(chloromethyl)amine, di(bromomethyl)amine,di(iodomethyl)amine, di(difluoromethyl)amine, di(dichloromethyl)amine,di(dibromomethyl)amine, di(diiodomethyl)amine, di(trifluoromethyl)amine,di(trichloromethyl)amine, di(tribromomethyl)amine,di(triiodomethyl)amine, di(2,2,2-trifluoroethyl)amine,di(2,2,2-trichloroethyl)amine, di(2,2,2-tribromoethyl)amine,di(2,2,2-triiodoethyl)amine, di(2,2,3,3,3-pentafluoroopropyl)amine,di(2,2,3,3,3-pentachloropropyl)amine,di(2,2,3,3,3-pentabromopropyl)amine, di(2,2,3,3,3-pentaiodopropyl)amine,di(2,2,2-trifluoro-1-trifluoromethylethyl)amine,di(2,2,2-trichloro-1-trichloromethylethyl)amine,di(2,2,2-tribromo-1-tribromomethylethyl)amine,di(2,2,2-triiodo-1-triiodomethylethyl)amine,di(1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl)amine,di(1,1,1,3,3,3-hexachloro-2-trichloromethylpropyl)amine,di(1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl)amine,di(1,1,1,3,3,3-hexaiodo-2-triiodomethylpropyl)amine,di(2-fluorophenyl)amine, di(3-fluorophenyl)amine,di(4-fluorophenyl)amine, di(2-chlorophenyl)amine,di(3-chlorophenyl)amine, di(4-chlorophenyl)amine,di(2-bromophenyl)amine, di(3-bromophenyl)amine, di(4-bromophenyl)amine,di(2-iodophenyl)amine, di(3-iodophenyl)amine, di(4-iodophenyl)amine,di(2,6-difluorophenyl)amine, di(3,5-difluorophenyl)amine,di(2,6-dichlorophenyl)amine, di(3,5-dichlorophenyl)amine,di(2,6-dibromophenyl)amine, di(3,5-dibromophenyl)amine,di(2,6-diiodophenyl)amine, di(3,5-diiodophenyl)amine,di(2,4,6-trifluorophenyl)amine, di(2,4,6-trichlorophenyl)amine,di(2,4,6-tribromophenyl)amine, di(2,4,6-triiodophenyl)amine,di(pentafluorophenyl)amine, di(pentachlorophenyl)amine,di(pentabromophenyl)amine, di(pentaiodophenyl)amine,di(2-(trifluoromethyl)phenyl)amine, di(3-(trifluoromethyl)phenyl)amine,di(4-(trifluoromethyl)phenyl)amine,di(2,6-di(trifluoromethyl)phenyl)amine,di(3,5-di(trifluoromethyl)phenyl)amine,di(2,4,6-tri(trifluoromethyl)phenyl)amine, di(2-cyanophenyl)amine,di(3-cyanophenyl)amine, di(4-cyanophenyl)amine, di(2-nitrophenyl)amine,di(3-nitrophenyl)amine, di(4-nitrophenyl)amine and the like. There canalso be exemplified phosphine compounds wherein the nitrogen atom isreplaced with a phosphorous atom. Those phosphine compounds arecompounds represented by replacing amine of the above specific exampleswith phosphine.

Specific examples of the alcohols described as for the compound(c)include fluoromethanol, chloromethanol, bromomethanol, iodomethanol,difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol,trifluoromethanol, trichloromethanol, tribromomethanol, triiodomethanol,2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol,2,2,2-triiodoethanol, 2,2,3,3,3-pentafluoropropanol,2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol,2,2,3,3,3-pentaiodopropanol, 2,2,2-trifluoro-1-trifluoromethylethanol,2,2,2-trichloro-1-trichloromethylethanol,2,2,2-tribromo-1-tribromomethylethanol,2,2,2-triiodo-1-triiodomethylethanol,1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol,1,1,1,3,3,3-hexachloro-2-trichloromethylpropanol,1,1,1,3,3,3-hexabromo-2-tribromomethylpropanol,1,1,1,3,3,3-hexaiodo-2-triiodomethylpropanol and the like. There canalso be exemplified thiol compounds wherein the oxygen atom is replacedwith a sulfur atom. Those thiol compounds are compounds represented byreplacing methanol of the above specific examples with methanethiol,replacing ethanol with ethanethiol and replacing propanol withpropanethiol, respectively, and the like.

Specific examples of the phenols described as for the compound(c)include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol,3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol,4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol,2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol,3,5-dichlorophenol, 2,6-dibromophenol, 3,5-dibromophenol,2,6-diiodophenol, 3,6-diiodophenol, 2,4,6-trifluorophenol,2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol,pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol,2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol,4-(trifluoromethyl)phenol, 2,6-di(trifluoromethyl)phenol,3,5-di(trifluoromethyl)phenol, 2,4,6-tri(trifluoromethyl)phenol,2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol,3-nitrophenol, 4-nitrophenol and the like. There can also be exemplifiedthiophenol compounds wherein the oxygen atom is substituted with asulfur atom. Those thiophenol compounds are compounds represented bysubstituting phenol of the above specific examples with thiophenol.

Specific examples of the carboxylic acids described as for thecompound(c) include 2-fluorobenzoic acid, 3-fluorobenzoic acid,4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoicacid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid,2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid,2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid,2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid,2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoroaceticacid, difluoroacetic acid, trifluoroacetic acid,pentafluoroethylcarboxylic acid, heptafluoropropylcarboxylic acid,1,1,1,3,3,3-hexafluoro-2-propylcarboxylic acid and the like.

Specific examples of the sulfonic acids as for the compound(c) includefluoromethanesulfonic acid, difluoromethanesulfonic acid,trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid,heptafluoropropanesulfonic acid,1,1,1,3,3,3-hexafluoro-2-propanesulfonic acid and the like.

Preferred examples of the amines as for the compound(c) includedi(trifluoromethyl)amine, di(2,2,2-trifluoroethyl)amine,di(2,2,3,3,3-pentafluoropropyl)amine,di(2,2,2-trifluoro-1-trifluoromethylethyl)amine,di(1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl)amine anddi(pentafluorophenyl)amine; preferred examples of the alcohols includetrifluoromethanol, 2,2,2-trifluoroethanol,2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanoland 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol; preferred examplesof the phenols include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol,2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol,pentafluorophenol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol,4-(trifluoromethyl)phenol, 2,6-di(trifluoromethyl)phenol,3,5-di(trifluoromethyl)phenol and 2,4,6-tri(trifluoromethyl)phenol;preferred examples of the carboxylic acids include pentafluorobenzoicacid and trifluoroacetic acid; and preferred examples of the sulfonicacids include trifluoromethanesulfonic acid.

More preferred examples of the compound(c) includedi(trifluoromethyl)amine, di(pentafluorophenyl)amine, trifluoromethanol,2,2,2-trifluoro-1-trifluoroethanol,1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 4-fluorophenol,2,6-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol,4-(trifluoromethyl)phenol, 2,6-di(trifluoromethyl)phenol and2,4,6-tri(trifluoromethyl)phenol, more preferably pentafluorophenol or1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol (common use name:perfluoro-tert-butanol).

(A) Modified Particles

The modified particles of the present invention is obtained bycontacting dry particles(a) with an organometallic compound(b), and thena compound(c) having a functional group containing active hydrogen or anon-proton donative Lewis basic functional group and an electronattractive group.

It is preferable that the contact treatment of (a) with (b), andsubsequent contact treatment with (c) are carried out under an inert gasatmosphere.

The treating temperature is normally within the range from −80 to 200°C., preferably from −20 to 150° C., and more preferably from 0 to 100°C. The treating time is normally from 1 minute to 48 hours, andpreferably from 10 minutes to 24 hours. It is preferred to use a solventand the solvent used is preferably an aliphatic or aromatic hydrocarbonsolvent, which is inert to (a), (b) and (c). Examples of the aliphatichydrocarbon solvent include butane, pentane, hexane, heptane, octane andthe like; and examples of the aromatic hydrocarbon solvent includebenzene, toluene, xylene and the like. There can also be used thoseobtained by optionally mixing these hydrocarbon solvents.

In the case of the contact of (a) with (b), and the subsequent contactwith (c), the method of contacting (a) with (b), and the method of thefollowing contacting with (c) may be the same or different.

The contact treated particles in each contacting step may be notsubjected to isolation operation, but it is preferable to isolate eachthe treated particles after each of contact of (a) with (b), and contactof thus contact-treated particles with (c), respectively. As examples ofthe isolating method, there can be included a method of decantation ofthe supernatant of the reaction solution, method of washing the treatedparticles with an inert solvent after filtration, method of washing thetreated particles with an inert solvent after filtration and drying themunder reduced pressure or an inert gas flow, method of distilling offthe solvent of the reaction solution under reduced pressure or an inertgas flow, and the like. Alternatively, when the isolation of the treatedparticles obtained as described above is not conducted, the particlesobtained in the reaction liquid may be used in the polymerization in astate of being suspended in the inert solvent.

Regarding the amount of (b) to (a) in the preparation of the modifiedparticles of the present invention, the metal atom of the organometalliccompound(b) contained in the particles obtained by contacting (a) with(b) is preferably not less than 0.1 mmol, and more preferably 0.5 to 20mmol, in terms of the number of mol of the metal atom contained in 1 gof the particles in the dry state. Regarding the amount of (c), themolar ratio of the compound(c) having a functional group containingactive hydrogen or a non-proton donative Lewis basic functional group,and an electron attractive group to the organometallic compound (b)contained in 1 g of particles in the dry state, i.e. (c)/(b), ispreferably from 0.01 to 100, more preferably from 0.05 to 5, and mostpreferably from 0.1 to 2.

The modified particles of the present invention can be used as a carrierfor supporting a catalyst component for olefin polymerization, such as atransition metal compound, and is suitably used in the polymerizationaccompanying formation of polymer particles. The modified particles ofthe present invention can functions as a catalyst component for olefinpolymerization. Examples of the catalyst for olefin polymerization usingthe modified particles of the present include those obtained by usingmodified particles(A) and a transition metal compound(B), and thoseobtained using modified particles(A), a transition metal compound(B) andan organometallic compound(C).

(B) Transition Metal Compound

The transition metal compound used in the present invention may be anytransition metal compound having olefin polymerization activity, and thetransition metal is preferably a transition metal of the 4th Group orlanthanide series of the Periodic Table of the Elements (1993, IUPAC).The transition metal compound is a metallocene transition metalcompound, more preferably.

The metallocene transition metal compound is, for example, a compoundrepresented by the following general formula (3):

ML_(a)R³ _(p−a)  (3)

(wherein M represents a transition metal of the 4th Group or lanthanideseries of the Periodic Table of the Elements (1993, IUPAC); L representsa group having a cyclopentadiene type anion skeleton or a group having ahetero atom, at least one of which is a group having a cyclopentadienetype anion skeleton, and a plurality of L may be the same or differentand may be crosslinked each other; R³ represents a hydrocarbon grouphaving 1 to 20 carbon atoms; a represents a number satisfying theexpression 0<a≦p; and p represents a valence of a transition metal atomM).

In the general formula (3) representing the metallocene transition metalcompound, M is a transition metal of the 4th Group or lanthanide seriesof the Periodic Table of the Elements (1993, IUPAC). Specific examplesof the transition metal of the 4th Group include titanium atom,zirconium atom, hafnium atom and the like; and examples of thetransition metal atom of lanthanide series include samarium and thelike. Among them, titanium atom, zirconium atom or hafnium atom ispreferred.

In the general formula (3) representing the metallocene transition metalcompound, L is a group having a cyclopentadiene type anion skeleton or agroup having a hetero atom, at least one of which is a group having acyclopentadiene type anion skeleton. A plurality of L may be the same ordifferent and may be crosslinked each other. Examples of the a grouphaving a cyclopentadiene type anion skeleton include η⁵-cyclopentadienylgroup, η⁵-substituted-cyclopentadienyl or polycyclic group having acyclopentadiene type anion skeleton. Examples of the substituent of theη⁵-substituted cyclopentadienyl group include hydrocarbon group having 1to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbonatoms or silyl group having 1 to 20 carbon atoms. Examples of thepolycyclic group having a cyclopentadiene form anion skeleton includeη⁵-indenyl group, η⁵-fluorenyl group and the like.

Examples of the hetero atom in the group having a hetero atom include anitrogen atom, phosphorus atom, oxygen atom, sulfur atom and the like.Examples of the group having such a hetero atom include hydrocarbonamino group, hydrocarbon phosphino group, hydrocarbon oxy group,hydrocarbon thio group and the like, and preferred examples thereofinclude alkoxy group, aryloxy group, alkylthio group, arylthio group,dialkylamino group, diarylamino group, dialkylphosphino group ordiarylphosphino group.

Specific examples of the η⁵-substituted-cyclopentadienyl group includeη⁵-methylcyclopentadienyl group, η⁵-ethylcyclopentadienyl group,η⁵-n-propylcyclopentadienyl group, η⁵-isopropylcyclopentadienyl group,η⁵-n-butylcyclopentadienyl group, η⁵-isobutylcyclopentadienyl group,η⁵-sec-butylcyclopentadienyl group, η⁵-tert-butylcyclopentadienyl group,η⁵-1,2-dimethylcyclopentadienyl group, η⁵-1,3-dimethylcyclopentadienylgroup, η⁵-1,2,3-trimethylcyclopentadienyl group,η⁵-1,2,4-trimethylcyclopentadienyl group, η⁵-teramethylcyclopentadienylgroup, η⁵-pentamethylcyclopentadienyl group,η⁵-trimethylsilylcyclopentadienyl group and the like.

Specific examples of the polycyclic group having a cyclopentadiene typeanion skeleton include η⁵-indenyl group, η⁵-2-methylindenyl group,η⁵-4-methylindenyl group, η⁵-4,5,6,7-tetarhydroindenyl group,η⁵-fluorenyl group and the like.

Specific examples of the group having a hetero atom include methoxygroup, ethoxy group, propoxy group, butoxy group, phenoxy group,thiomethoxy group, dimethylamino group, diethylamino group,dipropylamino group, dibutylamino group, diphenylamino group, pyrrolylgroup, dimethylphisphino group and the like.

Groups having a cyclopentadiene type anion skeleton, or a group having acylopentadienyl group and a group having a hetero atom may becrosslinked. In that case, an alkylene group such as ethylene group,propylene group or the like, a substituted alkylene group such asdimethylmethylene group, diphenylmethylene group or the like, or asubstituted silylene group such as silylene group, dimethylsilylenegroup, diphenylsilylene group, tetramethyldisilylene group or the likemay be lie therebetween.

R³ in the general formula (3) representing the metallocene transitionmetal compound is a halogen atom or a hydrocaron group having 1 to 20carbon atoms a is a number satisfying the expression 0<a≦p and p is avalence of a transition metal atom M). Specific examples of R³ includehalogen atom such as fluorine atom, chlorine atom, bromine atom, iodineatom or the like; and hydrocarbon group having 1 to 20 carbon atoms suchas methyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, phenyl group, benzyl group and the like. Preferred examples of R³include chlorine atom, methyl group or benzyl group.

Among the metallocene transition metal compounds represented by theabove general formula (3), specific examples of the compound wherein thetransition metal atom M is a zirconium atom, includebis(cyclopentadienyl)zirconium dichloride,bis(n-butylcyclopentadienyl)zirconium dichloride,bis(1,3-dimethylcyclopentadienyl)zirconium dichloride,bis(methylcyclopentadienyl)zirconium dichloride,bis(pentamethylcyclopentadienyl)zirconium dichloride,bis(indenyl)zirconium dichloride,bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)zirconiumdichloride, ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,ethylenebis(2-methylindenyl)zirconium dichloride,isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,dimethylsilylenebis(cyclopentadienyl)zirconium dichloride,dimethylsilylenebis(indenyl)zirconium dichloride,dimethylsilylenebis(2-methylindenyl)zirconium dichloride,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,dimethylsilylenebis(cyclopentadienyl)(fluorenyl)zirconium dichloride,diphenylsilylenebis(indenyl)zirconium dichloride,(cyclopentadienyl)(dimethylamide)zirconium dichloride,(cyclopentadienyl)(phenoxy)zirconium dichloride,dimethylsilylene(tert-butylamide)(tetramethylcyclopentadienyl)zirconiumdichloride, bis(cyclopentadienyl)zirconium dimethyl,bis(methylcyclopentadienyl)zirconium dimethyl,bis(pentamethylcyclopentadienyl)zirconium dimethyl,bis(indenyl)zirconium dimethyl, bis(4,5,6,7-tetrahydroindenyl)zirconiumdimethyl, bis(fluorenyl)zirconium dimethyl,ethylenebis(indenyl)zirconium dimethyl,dimethylsilylene(tert-butylamide)(tetramethylcyclopentadienyl)zirconiumdimethyl and the like.

There can also be exemplified compounds wherein zirconium is replacedwith titanium or hafnium in the above zirconium compounds.

These metallocene transition metal compounds may be used alone or incombination thereof.

(C) Organoaluminum Compound

As the organoaluminum compound(C) used in the present invention, apublicly known organoaluminum compound can be used. Preferably, it is anorganoaluminum compound represented by the general formula (4) R⁴_(b)AlY_(3−b) (wherein R⁴ represents a hydrocarbon group having 1 to 8carbon atoms; Al represents an aluminum atom; Y represents a hydrogenatom and/or halogen atom; and b represents a number satisfying 0<b≦3).

Specific examples of R⁴ in the general formula (4) representing theorganoaluminum compound include a methyl group, ethyl group, n-propylgroup, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexylgroup, n-octyl group and the like. Among them, an ethyl group, n-butylgroup, isobutyl group and n-hexyl group are preferred. Specific examplesof the halogen atom as for Y include fluorine atom, chlorine atom,bromine atom and iodine atom, preferably a chlorine atom.

Specific examples of the organoaluminum compound represented by thegeneral formula (4) R⁴ _(b)AlY_(3−b) include trialkylaluminums such astrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like; dialkylaluminum chlorides such asdimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminumchloride, di-n-butylaluminum chloride, diisobutylaluminum chloride,di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides suchas methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminumdichloride, n-butylaluminum dichloride, isobutylaluminum dichloride,n-hexylaluminum dichloride and the like; dialkylaluminum hydride such asdimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminumhydride, di-n-butylaluminum hydride, diisobutylaluminum hydride,di-n-hexylaluminum hydride and the like. Among them, trialkylaluminumsare preferred, and trimethylaluminum, triethylaluminum,tri-n-butylaluminum, triisobutylaluminum and tri-n-hexylaluminum aremore preferred and triisobutylaluminum and tri-n-hexylaluminum are mostpreferred.

These organoaluminum compounds may be used alone or in combinationthereof.

The catalyst for olefin polymerization of the present inventioncomprises modified particles (A) and a transition metal compound(B) andoptionally an organometallic compound(C). The amount of the component(B)is normally from 1×10⁻⁶ to 1×10⁻³ mol, and preferably from 5×10⁻⁶ to5×10⁻⁴ mol, per 1 g of the component(A). And, the amount of theorganometallic compound as the component(C) is preferably from 0.01 to10,000, more preferably from 0.1 to 5,000, and most preferably from 1 to2,000 in terms of molar ratio of the metal atom of the organometalliccompound as the compound(c) to the transition metal atom of thetransition metal compound as the component(B), i.e. (C)/(B).

In the present invention, the component(A) and component(B) andoptionally component(C) can be charged in a reactor in an arbitraryorder at the time of polymerization. Alternatively, these arbitrarycomponents in an arbitrary combination may be charged in the reactorafter previously bringing into contact with each other.

As a monomer used in the polymerization in the present invention, anyolefins and diolefins, having 2 to 20 carbon atoms, etc. can be used.Two or more olefins can also be used, simultaneously. The monomers areexemplified blow, but the present invention is not to the compoundsdescribed below. Specific examples of the olefin include α-olefinshaving 3 to 20 hydrocarbon atoms such as ethylene, propylene, butene-1,pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene1,4-methyl-1-pentene and the like, and olefins such as vinylcyclohexaneand the like. Diolefins include conjugated dienes and non-conjugateddienes, and specific examples of the compounds include 1,5-hexadiene,1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,5-vinyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene,1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene and the likeas a non-conjugated diene, and 1,3-butadiene, isoprene, 1,3-hexadiene,1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene and the like as aconjugated diene.

As a combination of monomers constituting a copolymer, combinations ofethylene and α-olefins described above (for example, ethylene andpropylene, ethylene and butene-1, ethylene and hexene-1) are preferable,and further, combinations of α-olefins (for example, propylene andbutene-1 and the like) are also exemplified, but the present inventionshould not be limited to the above compounds.

In the present invention, an aromatic vinyl compound can also be used asthe monomer. Specific examples of the aromatic vinyl compound includestyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,divinylbenzene and the like.

The polymerization method is not particularly limited, and there can beused gas phase polymerization in a gaseous monomer, solutionpolymerization using a solvent, slurry polymerization or the like.Examples of the solvent used in the solution polymerization or slurrypolymerization include aliphatic hydrocarbon solvents such as butane,pentane, heptane, octane and the like; aromatic hydrocarbon solventssuch as benzene, toluene and the like; halogenated hydrocarbon solventssuch as methylene chloride and the like. It is also possible to use theolefin itself as the solvent. The polymerization method may bebatch-wise polymerization or continuous polymerization and, furthermore,the polymerization may be performed in two or more stages underdifferent reaction conditions, respectively. The polymerization time isappropriately determined according to the kind of the desired olefinpolymer and reaction apparatus, but can be within the range from 1minute to 20 hours.

The present invention can be applied to the polymerization accompanyingformation of polymer particles (e.g. slurry polymerization, gas phasepolymerization, etc.), particularly preferably.

The slurry polymerization may be performed according to a publicly knownslurry polymerization method and polymerization conditions.

According to the preferred polymerization method in the slurry method,there is used a continuous type reactor wherein a monomer (comonomer), afeed and a diluent are optionally added and a polymer product is takenout, continuously or periodically. As the reactor, there is used a loopreactor or a plurality of stirring reactors, having different reactorsor reaction conditions, connected in series or parallel or a combinationthereof

As the diluent, there can be used an inert diluent (medium) such as aparaffin, cycloparaffin or aromatic hydrocarbon. The temperature of thepolymerization reactor or reaction zone is normally within the rangefrom about 50 to about 100° C., and preferably from 60 to 80° C. Thepressure can normally vary within the range from about 0.1 to about 10MPa, and preferably from 0.5 to 5 MPa. There can be set to the pressureat which a catalyst can be maintained in the suspended state and amedium and at least a part of a monomer and a comonomer can bemaintained in the sate of a liquid phase and, furthermore, the monomerand comonomer can be contacted therewith. Accordingly, the medium,temperature and pressure may be selected so that the olefin polymer isformed as solid particles and is recovered in that form.

The molecular weight of the olefin polymer can be controlled by publiclyknown means such as control of the temperature of the reaction zone,introduction of hydrogen or the like.

The respective catalyst components and monomer (and comonomer) can beadded to the reactor or reaction zone by a publicly known arbitrarymethod in arbitrary order. For example, there can be used a method ofadding the respective catalyst components and monomer (and comonomer) tothe reaction zone, simultaneously or successively. If desired, therespective catalyst components can be previously contacted with eachother in an inert atmosphere prior to contact with the monomer (andcomonomer).

The gas phase polymerization may be performed according to a publiclyknown gas phase polymerization method and polymerization conditions, butis not limited thereto. As the gas phase polymerization apparatus, therecan be used a fluidized bed type reactor, preferably a fluidized bedtype reactor having an extended portion. A reaction apparatus equippedwith a stirring blade in a reactor may also be used with no problem.

As the method of feeding the respective components to the polymerizationreactor, there can be used a method of feeding them in the absence ofwater using an inert gas (e.g. nitrogen, argon), hydrogen, ethylene orthe like, or a method of feeding them in the form of a solution orslurry dissolved or diluted in a solvent. The respective catalystcomponents may be separately fed, or fed after previously contacting thearbitrary components with each other in an arbitrary order.

Regarding the polymerization conditions, the temperature is lower thanthe temperature at which the polymer is molten, preferably from 20 to100° C., and particularly preferably from 40 to 90° C. The pressure ispreferably within the range from 0.1 to 5 MPa, and more preferably from0.3 to 4 MPa. Furthermore, hydrogen may also be added as a molecularweight modifier for the purpose of controlling the melt fluidity of thefinal product. In case of the polymerization, an inert gas may coexistin a mixed gas.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a flow chart for assisting the understanding of the presentinvention. This flow chart is a typical example of an embodiment of thepresent invention, and the present invention is not limited thereto.

BEST MODE FOR PRACTICING THE INVENTION

The present invention is explained by Examples and Comparative Examplesin more detail below but is not limited thereto. Properties of olefinpolymers in the Examples were measured by the following methods.

(1) Content of α-olefin in Copolymer

The content of an α-olefin in the obtained copolymer was determined fromits infrared absorption spectrum. The measurement and calculation werecarried out according to the method described in the literature(Characterization of Polyethylene by Infrared Absorption Spectrum,authored by Takayama and Usami et al.; or Die Makromoleculare Chemie,177, 461(1976) McRae, M. A., Madams, W. F.) utilizing characteristicabsorption derived from α-olefin, e.g. 1375 cm⁻¹ (propylene) and 772cm⁻¹. The infrared absorption spectrum was measured by using an infraredspectrometer (FT-IR7300, manufactured by Nippon Bunko Kogyo Co.). Theshort chain branch (SCB) was represented as a short chain branch numberper 1000 carbon atoms.

(2) Melting Point of Copolymer

It was measured under the following conditions by using Seiko SSC-5200.

Heating: heating from 40 to 150° C. (10° C./min.) and maintaining for 5minutes

Cooling: cooling from 150 to 40° C. (5° C./min.) and maintaining for 10minutes

Measurement: measured at the temperature within the range from 40 to160° C. (5° C./min.)

(3) Intrinsic Viscosity [η]

100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at135° C., and then the intrinsic viscosity was determined from a droppingrate of a tetralin solution obtained by dissolving said sample by usingan Ubbelohde viscometer set in an oil bath maintained at 135° C.

(4) Molecular Weight and Molecular Weight Distribution

They were determined under the following conditions by using gelpermeation chromatograph (150, C, manufactured by Waters Co.). Themolecular weight distribution (Mw/Mn) was represented as a ratio of theweight average molecular weight(Mw) to the number average molecularweight(Mn).

Column: TSK gel GMH-HT

Measuring temperature: set at 145° C.

Measuring concentration: 10 mg/10 ml ortho-dichlorobenzene

(5) MFR

It was measured at 190° C. according to the method defined in JIS K6760.

(6) Density

It was determined according to JIS K-6760. The value of density (withoutannealing) is a value of density measured without annealing, and thevalue of density (with annealing) is a value of density measured afterannealing treatment. Unit:g/cM³.

EXAMPLE 1

(1) Contact Treatment of Particles (a) with Organometallic Compound(b)

The atmosphere in a 200 ml four necked flask equipped with a stirrer, adropping funnel and a thermometer was dried under reduced pressure andthen replaced with nitrogen. 5.51 g of silica (manufactured by CROSFIELDCo., Ltd., ES70X, average diameter: 48.0 μm, pore volume: 1.61 ml/g,specific surface area: 290 m²/g) heat-treated under a nitrogen flow at300° C. for 5 hours was charged in the flask. Then, 100 ml of toluenewas added to form a slurry, the slurry was cooled to 5° C. in an icebath and 11.0 ml of a toluene solution of trimethylaluminum whoseconcentration was adjusted to 1 mmol/ml was slowly added dropwisethereto. In that case, a gas was evolved. After stirring at 5° C. for 30minutes, then at 80° C. for 2 hours, the supernatant was removed byfiltration and the residual solid compound was washed four times with100 ml of toluene and then washed twice with 100 ml of hexane.Thereafter, the solid compound was dried under reduced pressure toobtain 5.54 g of a flowable solid compound.

(2) Compound (c) Treatment

The atmosphere in a 100 ml four neck flask equipped with a stirrer and athermometer was dried under reduced pressure and then replaced bynitrogen. 1.05 g of the solid compound obtained in the (1) describedabove was charged in the flask. Then, 50 ml of toluene was added to forma slurry and 2.1 ml of a toluene solution of pentafluorophenol whoseconcentration was adjusted to 1 mmol/ml was slowly added. In that case,a gas was evolved. After stirring at room temperature for 30 minutes,then at 80° C. for 2 hours, the supernatant was removed by filtrationand the residual solid compound was washed four times with 50 ml oftoluene and then washed twice with 50 ml of hexane. Thereafter, thesolid compound was dried under reduced pressure to obtain 1.13 g of aflowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 95 g of butane and 5 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system became stable, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 2 μmol/ml was charged and 35.7 mg of the solid compoundobtained in the (2) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 38.4 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 7.7×10⁷ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 2150 g/g hour.The resulting olefin polymer has SCB of 21.1, a melting point of 110.3°C. and 119.6° C. and [η] of 1.87.

Comparative Example 1

(1) Contact Treatment Between Dry Particles and Organometallic Compound

The atmosphere in a 200 ml four neck flask equipped with a stirrer, adropping funnel and a thermometer was dried under reduced pressure andthen replaced with nitrogen. 9.26 g of silica (manufactured by CROSFIELDCo., Ltd., ES70X) heat-treated under a nitrogen flow at 300° C. for 5hours was charged in the flask. Then, 92.6 ml of toluene was added toform a slurry,. which was cooled to 5° C. in an ice bath and 18.5 ml ofa toluene solution of trimethylaluminum whose concentration was adjustedto 1 mmol/ml was slowly added dropwise. In that case, a gas was evolved.After stirring at 5° C. for 30 minutes, then at room temperature for 2hours, the supernatant was removed by filtration and the residual solidcompound was washed four times with 100 ml of toluene and then washedtwice with 100 ml of hexane. Thereafter, the solid compound was driedunder reduced pressure to obtain 9.92 g of a flowable solid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 95 g of butane and 5 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 30.0 mg of the solid compoundobtained in the above item (1) was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, an olefin polymer was not obtained.

Comparative Example 2

(1) Contact Treatment Between Undried Particles and OrganometallicCompound

The atmosphere in a 100 ml four neck flask equipped with a stirrer, adropping funnel and a thermometer was dried under reduced pressure andthen replaced with nitrogen. 2.00 g of non-heat-treated silica(manufactured by CROSFIELD Co., Ltd., ES70X) was charged in the flask.Then, 50 ml of toluene was added to form a slurry, which was cooled to5° C. in an ice bath and 8.0 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at room temperature for 2 hours, thesupernatant was removed by filtration and the residual solid compoundwas washed four times with 150 ml of toluene and then washed twice with50 ml of hexane. Thereafter, the solid compound was dried under reducedpressure to obtain 2.31 g of a flowable solid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 95 g of butane and 5 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 2 μmol/ml was charged and 29.2 mg of the solid compoundobtained in the (1) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 0.118 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 3.8×10⁵ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 12.9 g/g hour.

It is considered that, regarding the solid compound obtained in the (1)above, methylaluminoxane was produced by reacting water remained insilica with trimethylaluminum (additional test of Japanese PatentKokai(Unexamined) No. 1-207303). Unlike Comparative Example 1 usingdried silica, the polymerization activity was shown but was lower thanthat of Example 1.

Comparative Example 3

(1) Synthesis of Aluminum Compound Having Electron Attractive Group

A 100 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 30 ml of toluene and 20 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wereadded in the flask. After cooling to not more than 5° C. in an ice bath,20 ml of a toluene solution of pentafluorophenol whose concentration wasadjusted to 2 mmol/ml was added dropwise. After completion of thedropwise addition, the solution was stirred at 5° C. for 30 minutes,then at room temperature for 5 hours. After the solvent was distilledoff until the amount of the solution was reduced to half, the solutionwas concentrated, cooled and then re-crystallized. As a result, 2.70 gof MeAl(OC₆F₅)₂ was obtained as a white crystal. The yield was 34.4%.

(2) Contact Treatment Between Dried Particles and OrganometallicCompound Having Electron Attractive Group

A 100 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 1.16 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 50 ml of toluene was added to form a slurry, and 2.0 mlof a toluene solution of MeAl(OC₆F₅)₂ (2 mmol/ml synthesized in the (1)described above was slowly added dropwise. In that case, a gas wasevolved. After stirring at room temperature for 30 minutes, then at 8°C. for 2 hours, the supernatant was removed by filtration and theresidual solid compound was washed four times with 50 ml of toluene andthen washed twice with 50 ml of hexane. Thereafter, the solid compoundwas dried under reduced pressure to obtain 1.39 g of a flowable solidcompound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 95 g of butane and 5 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol /ml was charged and 36.2 mg of the solid compoundobtained in the (2) above was charged as the solid catalyst component.The polymerization was carried out at 70° C. for 30 minutes whilefeeding ethylene so that the total pressured is held constant. As aresult, 32.2 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 6.4×10⁷ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 1780 g/g hour.The resulting olefin polymer has SCB of 20.1, a melting point of 111.7°C. and 117.4° C. and [η] of 1.82.

EXAMPLE 2

(1) Contact Treatment Between Particles (a) and Organometallic Compound(b)

A 500 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 45.0 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 250 ml of toluene was added to form a slurry, which wascooled to 5° C. in an ice bath and 90.0 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at 80° C. for 2 hours, the supernatant wasremoved by filtration and the residual solid compound was washed fourtimes with 250 ml of toluene and then washed twice with 250 ml ofhexane. Thereafter, the solid compound was dried under reduced pressureto obtain 46.0 g of a flowable solid compound.

(2) Compound (c) Treatment

A 500 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 37.2 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 222 ml of toluene was added to form a slurry and 37.2ml of a toluene solution of pentafluorophenol whose concentration wasadjusted to 2 mmol/ml was slowly added dropwise. In that case, a gas wasevolved. After stirring at room temperature for 30 minutes, then at 80°C. for 2 hours, the supernatant was removed by filtration and theresidual solid compound was washed four times with 200 ml of toluene andthen washed twice with 200 ml of hexane. Thereafter, the solid compoundwas dried under reduced pressure to obtain 45.2 g of a flowable solidcompound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer wasdried under reduced pressure, then replaced with argon and evacuated,and 95 g of butane and 5 g of butene-1 were charged in the autoclave,followed by heating to 70° C. Ethylene was added so that its partialpressure became 6 kg/cm² and, after the system was stabilized, 0.25 mlof a heptane solution of triisobutylaluminum whose concentration wasadjusted to 1 mmol/ml was charged. Then, 0.2 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 12.2 mg of the solid compoundobtained in the (2) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 24.0 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 2.4×10⁸ g/mol zr. hour and thepolymerization activity per solid catalyst component was 3980 g/g hour.The resulting olefin polymer has SCB of 17.3, a melting point of 103.1°C. and [η] of 2.18.

EXAMPLE 3

(1) Contact Treatment Between Particles (a) and Organometallic Compound(b)

A 200 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 10.7 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 110 ml of toluene was added to form a slurry, which wascooled to 5° C. in an ice bath and 21.4 ml of a toluene solution oftriethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at room temperature for 2 hours, thesupernatant was removed by filtration and the residual solid compoundwas washed four times with 100 ml of toluene and then washed twice with100 ml of hexane. Thereafter, the solid compound was dried under reducedpressure to obtain 11.1 g of a flowable solid compound.

(2) Compound (c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 1.83 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 50 ml of toluene was added to form a slurry and 3.6 mlof a toluene solution of pentafluorophenol whose concentration wasadjusted to 1 mmol/ml was slowly added. In that case, a gas was evolved.After stirring at room temperature for 30 minutes, then at 80° C. for 2hours, the supernatant was removed by filtration and the residual solidcompound was washed four times with 50 ml of toluene and then washedtwice with 50 ml of hexane. Thereafter, the solid compound was driedunder reduced pressure to obtain 1.93 g of a flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 95 g of butane and 5 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 2 μmol/ml was charged and 43.4 mg of the solid compoundobtained in the (2) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 10 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 20.6 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 1.2×10⁸ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 2850 g/g hour.The resulting olefin polymer has SCB of 29.9, a melting point of 87.0°C. and 98.5° C., and [η] of 1.24.

EXAMPLE 4

(1) Contact Treatment Between Particles (a) and Organometallic Compound(b)

A 200 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 13.8 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 138 ml of toluene was added to form a slurry, which wascooled to 5° C. in an ice bath and 27.5 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at room temperature for 2 hours, thesupernatant was removed by filtration and the residual solid compoundwas washed four times with 100 ml of toluene and then washed twice with100 ml of hexane. Thereafter, the solid compound was dried under reducedpressure to obtain 13.8 g of a flowable solid compound.

(2) Compound (c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 2.10 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 50 ml of toluene was added to form a slurry and 4.2 mlof a toluene solution of pentafluorophenol whose concentration wasadjusted to 1 mmol/ml was slowly added. In that case, a gas was evolved.After stirring at room temperature for 30 minutes, then at 80° C. for 2hours, the supernatant was removed by filtration and the residual solidcompound was washed four times with 50 ml of toluene and then washedtwice with 50 ml of hexane. After washing, the solid compound was driedunder reduced pressure to obtain 2.28 g of a flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced by argon, was evacuated and 95 g of butane and 5 g of butene-1were charged in the autoclave, followed by heating to 70° C. Ethylenewas added so that its partial pressure became 6 kg/cm² and, after thesystem was stabilized, 0.25 ml of a heptane solution oftri-n-hexylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 2 μmol/ml was charged and 26.7 mg of the solid compoundobtained in the (2) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 23.5 g of an olefin polymer was obtained. Polymerizationactivity per transition metal atom was 4.7×10⁷ g/mol Zr. hour andpolymerization activity per solid catalyst component was 1760 g/g hour.The resulting olefin polymer has SCB of 17.1, a melting point of 106.3°C. and [η] of 1.80.

EXAMPLE 5

(1) Preparation of Particles (A)

A 50 ml four neck flask equipped with a stirrer, a dropping funnel and athermometer was dried under reduced pressure and then replaced withnitrogen. 1.89 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 10 ml of toluene was added to form a slurry, which wascooled to 5° C. in an ice bath and 3.8 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at 80° C. for 2 hours, the supernatant wasremoved by filtration and the residual solid compound was washed fourtimes with 10 ml of toluene. Then, 10 ml of toluene was added to form aslurry again and 3.8 ml of a toluene solution of pentafluorophenol whoseconcentration was adjusted to 1 mmol/ml was slowly added. Also in thiscase, a gas was evolved. After stirring at room temperature for 30minutes, then at 80° C. for 2 hours, the supernatant was removed byfiltration and the residual solid compound was washed four times with 10ml of toluene and then washed twice with 10 ml of hexane. After washing,the solid compound was dried under reduced pressure to obtain 2.35 g ofa flowable solid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 720 g of butane and 30 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 1.8 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 24.8 mg of the solid compoundobtained in the (1) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 60 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 75 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 1.5×10⁸ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 3030 g/g hour.The resulting olefin polymer has SCB of 22.4, a melting point of 98.8°C., [η] of 2.23.

EXAMPLE 6

(1) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 720 g of butane and 30 g ofbutene-1 were charged in the autoclave, followed by heating to 83° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 1.8 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 22.3 mg of the solid compoundobtained in the (1) described above was charged as the solid catalystcomponent. The polymerization was carried out at 83° C. for 60 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 41 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 8.2×10⁷ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 1840 g/g hour.The resulting olefin polymer has SCB of 26.5, a melting point of 101.3°C., [η] of 2.23 and MFR of 0.303 g/10 mim.

EXAMPLE 7

(1) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 720 of butane and 30 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² andhydrogen was added so that its partial pressure became 50 mmHg and,after the system was stabilized, 1.8 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 27.5 mg of the solid compoundobtained in Example 2(2) was charged as the solid catalyst component.The polymerization was carried out at 70° C. for 60 minutes whilefeeding ethylene so that the total pressured is held constant. As aresult, 28 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 5.6×10⁷ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 1020 g/g hour.The resulting olefin polymer has SCB of 26.4, melting points of 91.7° C.and 99.9° C., [η] of 1.31, Mw of 83200, Mn of 25600, Mw/Mn of 3.3 andMFR of 1.98 g/10 min.

EXAMPLE 8

(1) Preparation of Particles (A)

A 100 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 1.09 g of the solid compound obtained in Example 4(1) wascharged in the flask. Then, 50 ml of toluene was added to form a slurry,and 0.31 ml of perfluoro-tert-butylacohol was slowly added. In thatcase, a gas was evolved. After stirring at room temperature for 30minutes, then at 80° C. for 2 hours, the supernatant was removed byfiltration and the residual solid compound was washed four times with 50ml of toluene and then washed twice 50 ml of hexane. After washing, thesolid compound was dried under reduced pressure to obtain 1.20 g of aflowable solid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced by argon, was evacuated and 715 g of butane and 35 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 1.8 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 37.6 mg of the solid compoundobtained in the (1) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 60 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 124 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 1.2×10⁸ g/mol zr. hour and thepolymerization activity per solid catalyst component was 3300 g/g hour.The resulting olefin polymer has SCB of 19.2, a melting point of 103.5°C. and [η] of 2.39.

EXAMPLE 9

(1) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 715 g of butane and 35 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² andhydrogen was added so that its partial pressure became 100 mmHg and,after the system was stabilized, 1.8 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 g mol/ml was charged and 55.3 mg of the solid compoundobtained in the above item (1) of Example 8 was charged as the solidcatalyst component. The polymerization was carried out at 70° C. for 60minutes while feeding ethylene so that the total pressured is heldconstant. As a result, 21 g of an olefin polymer was obtained. Thepolymerization activity per transition metal atom was 2.1×10⁶ g/mol Zr.hour and the polymerization activity per solid catalyst component was380 g/g hour. The resulting olefin polymer has SCB of 30.8, a meltingpoint of 96.3° C., [η] of 1.20 and MFR of 0.89 g/10 min.

EXAMPLE 10

(1) Contact Treatment Between Particles (a) and Organometallic Compound(b)

A 200 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 9.25 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 92.5 ml of toluene was added to form a slurry, whichwas cooled to 5° C. in an ice bath and 18.5 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at room temperature for 2 hours, thesupernatant was removed by filtration and the residual solid compoundwas washed four times with 100 ml of toluene and then washed twice with100 ml of hexane. Thereafter, the solid compound was dried under reducedpressure to obtain 9.96 g of a flowable solid compound.

(2) Compound (c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 0.76 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 50 ml of toluene was added to form a slurry and 1.5 mlof a toluene solution of 2,3,5,6-tetrafluorophenol whose concentrationwas adjusted to 1 mmol/ml was slowly added. In that case, a gas wasevolved. After stirring at room temperature for 30 minutes, then at 80°C. for 2 hours, the supernatant was removed by filtration and theresidual solid compound was washed four times with 50 ml of toluene andthen washed twice with 50 ml of hexane. Thereafter, the solid compoundwas dried under reduced pressure to obtain 0.78 g of a flowable solidcompound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced by argon, was evacuated and 95 g of butane and 5 g of butene-1were charged in the autoclave, followed by heating to 70° C. Ethylenewas added so that its partial pressure became 6 kg/cm² and, after thesystem was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 38.5 g of the solid compoundobtained in the (2)described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 16.1 g of an olefin polymer was obtained. The Polymerizationactivity per transition metal atom was 3.2×10⁷ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 836 g/g hour.The resulting olefin polymer has SCB of 17.7, a melting point of 103.1°C. and 109.5° C. and [η] of 1.84.

EXAMPLE 11

(1) Preparation of Particles (A)

The atmosphere in a 100 ml four neck flask equipped with a stirrer, adropping funnel and a thermometer was dried under reduced pressure andthen replaced by nitrogen. 0.83 g of the solid compound obtained inExample 10(1) was charged in the flask. Then, 50 ml of toluene was addedto form a slurry, and 1.70 ml of 4-fluorophenol was slowly added. Inthat case, a gas was evolved. After stirring at room temperature for 30minutes, then at 80° C. for 2 hours, the supernatant was removed byfiltration and the residual solid compound was washed four times with 50ml of toluene and then washed twice 50 ml of hexane. Thereafter, thesolid compound was dried under reduced pressure to obtain 0.88 g of aflowable solid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 95 g of butane and 5 g ofbutene-1 were charged in the autoclave, followed by heating to 7° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 2 μ/mol/ml was charged and 29.1 mg of the solid compoundobtained in the (1) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 2.05 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 4.1×10⁶ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 141 g/g hour.The resulting olefin polymer has SCB of 21.1 and a melting point of99.9° C.

EXAMPLE 12

(1) Preparation of Particles (A)

A 100 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 0.90 g of the solid compound obtained in Example 10 (1) wascharged in the flask. Then, 50 ml of toluene was added to form a slurry,and 1.80 ml of a toluene solution of pentafluoroaniline whoseconcentration was adjusted to 1 mmol/ml was slowly added. In that case,a gas was evolved. After stirring at room temperature for 30 minutes,then at 80° C. for 2 hours, the supernatant was removed by filtrationand the residual solid compound was washed four times with 50 ml oftoluene and then washed twice 50 ml of hexane. Thereafter, the solidcompound was dried under reduced pressure to obtain 0.94 g of a flowablesolid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced by argon, was evacuated and 95 g of butane and 5 g of butene-1were charged in the autoclave, followed by heating to 70° C. Ethylenewas added so that its partial pressure became 6 kg/cm² and, after thesystem was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 0.5 ml of a toluene solution ofethylenebis(indenyl)zirconium dichloride whose concentration wasadjusted to 2 μmol/ml was charged and 32.2 mg of the solid compoundobtained in the (1) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 4.48 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 9.0×10⁶ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 278 g/g hour.The resulting olefin polymer has SCB of 23.0, a melting point of 99.5°C. and [η] of 1.70.

EXAMPLE 13

(1) Contact Treatment Between Particles (a) and Organometallic Compound(b)

A 200 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced bynitrogen. 4.92 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 50 ml of toluene was added to form a slurry, which wascooled to 5° C. in an ice bath and 10.0 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at room temperature for 2 hours, thesupernatant was removed by filtration and the residual solid compoundwas washed four times with 100 ml of toluene and then washed twice with100 ml of hexane. Thereafter, the solid compound was dried under reducedpressure to obtain 5.26 g of a flowable solid compound.

(2) Compound(c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced by nitrogen. 3.19 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 100 ml of toluene was added to form a slurry and 3.2 mlof a toluene solution of pentafluorophenol whose concentration wasadjusted to 2 mmol/ml was slowly added. In that case, a gas was evolved.After stirring at room temperature for 3 hours, the supernatant wasremoved by filtration and the residual solid compound was washed fourtimes with 50 ml of toluene and then washed twice with 50 ml of hexane.Thereafter, the solid compound was dried under reduced pressure toobtain 3.63 g of a flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 90 g of butane and 10 g ofbutene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofbis(cyclopentadienyl)zirconium dichloride whose concentration wasadjusted to 1 μmol/ml was charged and 36.7 mg of the solid compoundobtained in the (2) described above was charged as the solid catalystcomponent. The polymerization was carried out at 70° C. for 30 minuteswhile feeding ethylene so that the total pressured is held constant. Asa result, 4.64 g of an olefin polymer was obtained. The polymerizationactivity per transition metal atom was 9.3×10⁶ g/mol Zr. hour and thepolymerization activity per solid catalyst component was 252 g/g hour.The resulting olefin polymer has SCB of 19.8, a melting point of 96.7°C. and [η] of 2.48.

EXAMPLE 14

(1) Ethylene Polymerization

An autoclave (internal volume of 400 ml) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced by argon, was evacuated and 100 g of butane and 4 ml ofhexene-1 were charged in the autoclave, followed by heating to 70° C.Ethylene was added so that its partial pressure became 6 kg/cm² and,after the system was stabilized, 0.25 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml wascharged. Then, 1.0 ml of a toluene solution ofdimethylsilylene(tetramethylcyclopentadienyl)(tert-butylamide) titaniumdichloride whose concentration was adjusted to 1 μmol/ml was charged and20.0 mg of the solid compound obtained in Example 13 (2) was charged asthe solid catalyst component. The polymerization was carried out at 70°C. for 30 minutes while feeding ethylene so that the total pressured isheld constant. As a result, 1.40 g of an olefin polymer was obtained.The polymerization activity per transition metal atom was 2.8×10⁶ g/molZr. hour and the polymerization activity per solid catalyst componentwas 140 g/g hour. The resulting olefin polymer has SCB of 27.1, amelting point of 77.3° C. and 113.5° C.

EXAMPLE 15

(1) Contact Treatment Between Particles(a) and OrganometallicCompound(b)

A 200 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 9.26 g of silica (manufactured by CROSFIELD Co., Ltd., ES70X)heat-treated under a nitrogen flow at 300° C. for 5 hours was charged inthe flask. Then, 92.6 ml of toluene was added to form a slurry, whichwas cooled to 5° C. in an ice bath and 18.5 ml of a toluene solution oftrimethylaluminum whose concentration was adjusted to 1 mmol/ml wasslowly added dropwise. In that case, a gas was evolved. After stirringat 5° C. for 30 minutes, then at room temperature for 2 hours, thesupernatant was removed by filtration and the residual solid compoundwas washed four times with 100 ml of toluene and then washed twice with100 ml of hexane. Thereafter, the solid compound was dried under reducedpressure to obtain 9.92 g of a flowable solid compound.

(2) Treatment of Compound(c)

The atmosphere in a 100 ml four neck flask equipped with a stirrer and athermometer was dried under reduced pressure and then replaced bynitrogen. 5.45 g of the solid compound obtained in the (1) describedabove was charged in the flask. Then, 135 ml of toluene was added toform a slurry and 10.9 ml of a toluene solution of pentafluorophenolwhose concentration was adjusted to 1 mmol/ml was slowly added. In thatcase, a gas was evolved. After stirring at room temperature for 30minutes, then at 80° C. for 2 hours, the supernatant was removed byfiltration and the residual solid compound was washed four times with 50ml of toluene and then washed twice with 50 ml of hexane. Thereafter,the solid compound was dried under reduced pressure to obtain 6.11 g ofa flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 1 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was heated to 80° C. and evacuated. Then, 20 g ofNaCl powder was added and, furthermore, butene-1 and ethylene werecharged at a partial pressure of 560 mmHg and 11 kg/cm², respectively,thereby to make the system stable. 1.0 ml of a heptane solution oftriisobutylaluminum whose concentration was adjusted to 1 mmol/ml, 1.0ml of a toluene solution of ethylenebis(indenyl)zirconium dichloridewhose concentration was adjusted to 2 μmol /ml, 91.1 mg of the solidcompound obtained in the (2) described above as the solid catalystcomponent, and 0.5 ml of hexane were contacted each other under an argonatmosphere for 30 seconds, and the resulting mixture was charged in theabove autoclave. The polymerization was carried out at 80° C. for 1 hoursubstantially in the absence of a liquid while feeding a mixed gas ofethylene and butene-1 (content of butene-1: 6.3% by volume) so that thetotal pressured is held constant. The contents in the autoclave werewashed with water and then dried to obtain 39 g of an olefin polymer.The polymerization activity per transition metal atom was 2.0×10⁷ g/molZr. hour and the polymerization activity per solid catalyst componentwas 428 g/g hour. The resulting olefin polymer has SCB of 26.0, amelting point of 100.6° C., [η] of 1.61, Mw of 130,000, Mw/Mn of 4.4 andMFR of 0.33.

EXAMPLE 16

(1) Contact Treatment Between Particles(a) and OrganometallicCompound(b)

A 100 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 2.35 g of silica heat-treated at 300° C. (manufactured byDavison Co., Ltd., Sylopol 948; average diameter=55 μm; pore volume=1.66ml/g; specific surface area=304 m²/g; silica preserved under a nitrogenatmosphere after heat-treated at 300° C. by Davison Co., Ltd.) wascharged in the flask. Then, 40 ml of toluene was added to form a slurry,which was cooled to 5° C. in an ice bath, and a mixed solution of 4.7 mlof a heptane solution of trimethylaluminum whose concentration wasadjusted to 1 mmol/ml with 7 ml of toluene was slowly added dropwise. Inthat case, a gas was evolved. After stirring at 5° C. for 30 minutes,then at 80° C. for 2 hours, the supernatant was removed by filtrationand the residual solid compound was washed four times with 50 ml oftoluene and then washed twice with 50 ml of hexane. Thereafter, thesolid compound was dried under reduced pressure to obtain 2.73 g of aflowable solid compound.

(2) Compound (c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 2.44 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 40 ml of toluene was added to form a slurry, and amixed solution of 2.4 ml of a toluene solution of pentafluorophenolwhose concentration was adjusted to 1.6 mmol/ml with 7 ml of toluene wasslowly added. In that case, a gas was evolved. After stirring at roomtemperature for 30 minutes, then at 80° C. for 2 hours, the supernatantwas removed by filtration and the residual solid compound was washedfour times with 50 ml of toluene and then washed twice with 50 ml ofhexane. Thereafter, the solid compound was dried under reduced pressureto obtain a flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated, and hydrogen was added so that itspartial pressure became 60 mmHg, and 735 g of butane and 15 g ofbutene-1 were charged , followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 0.5 ml of atoluene solution of ethylenebis(2-methyl-indenyl)zirconium dichloridewhose concentration was adjusted to 2 μmol /ml was charged and 29.4 mgof the solid compound obtained in the (2) described above was charged asthe solid catalyst component. The polymerization was carried out at 70°C. for 60 minutes while feeding ethylene so that the total pressured isheld constant. As a result, 41.8 g of an olefin polymer was obtained.The polymerization activity per transition metal atom was 4.2×10⁷ g/molZr. hour and polymerization activity per solid catalyst. component was1420 g/g hour. The resulting olefin polymer has SCB of 19.8, [η] of1.30, Mw of 116000, Mn of 12000, Mw/Mn of 9.7, MFR of 1.41 g/10 min. anda density(without annealing) of 0.9154 g/cm³.

EXAMPLE 17

(1) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated, and hydrogen was added so that itspartial pressure became 20 mmHg, and 725 g of butane and 25 g ofbutene-1 were charged , followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 1 ml of atoluene solution of ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride whose concentration was adjusted to 1 μmol/ml was charged and32.5 mg of the solid compound obtained in Example 16(2) described abovewas charged as the solid catalyst component. The polymerization wascarried out at 70° C. for 60 minutes while feeding ethylene so that thetotal pressured is held constant. As a result, 43.5 g of an olefinpolymer was obtained. The polymerization activity per transition metalatom was 4.4×10⁷ g/mol Zr. hour and polymerization activity per solidcatalyst component was 1340 g/g hour. The resulting olefin polymer hasSCB of 16.0, [η] of 1.86, Mw of 110000, Mn of 40000, Mw/Mn of 2.8, MFRof 0.52 g/10 min. and a density(without annealing) of 0.9126 g/cm³.

EXAMPLE 18

(1) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated, and hydrogen was added so that itspartial pressure became 50 mmHg, and 735 g of butane and 15 g ofbutene-1 were charged followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 1 ml of atoluene solution of dimethylsilylenebis(2-methyl-indenyl)zirconiumdichloride whose concentration was adjusted to 1 μmol/ml was charged and28.0 mg of the solid compound obtained in Example 16(2) described abovewas charged as the solid catalyst component. The polymerization wascarried out at 70° C. for 60 minutes while feeding ethylene so that thetotal pressured was held constant. As a result, 65 g of an olefinpolymer was obtained. The polymerization activity per transition metalatom was 6.5×10⁷ g/mol Zr. hour and the polymerization activity persolid catalyst component was 2320 g/g hour. The resulting olefin polymerhas SCB of 17.6, a melting point of 101.0° C., Mw of 227000, Mn of59000, Mw/Mn of 3.8, and a density(without annealing) of 0.9058 g/cm³.

EXAMPLE 19

(1) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated and 720 g of butane and 30 g ofbutene-1 were charged, followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 1 ml of atoluene solution of bis(n-butylcyclopentadienyl) zirconium dichloridewhose concentration was adjusted to 1 μmol/ml was charged, and then 35.3mg of the solid compound obtained in Example 16(2) described above wascharged as the solid catalyst component. The polymerization was carriedout at 70° C. for 60 minutes while feeding ethylene so that the totalpressured was held constant. As a result, 45.5 g of an olefin polymerwas obtained. The polymerization activity per transition metal atom was4.6×10⁷ g/mol Zr. hour and the polymerization activity per solidcatalyst component was 1290 g/g hour. The resulting olefin polymer hasSCB of 21.4, [η] of 2.09, Mw of 125000, Mn of 67000, Mw/Mn of 1.9,MFR=0.36 g/10 min. and a density(without annealing) of 0.9055 g/cm³.

EXAMPLE 20

(1) Contact Treatment Between Particles(a) and OrganometallicCompound(b)

A 100 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 2.0 g of silica heat-treated at 300° C.(manufactured byDavison Co., Ltd., Sylopol 948; average diameter=55 μm; pore volume=1.66ml/g; specific surface area=304 m²/g; silica preserved under a nitrogenatmosphere after heat-treated at 300° C. by Davison Co., Ltd.) wascharged in the flask. Then, 40 ml of toluene was added to form a slurry,which was cooled to 5° C. in an ice bath, and a mixed solution of 4.0 mlof a heptane solution of trimethylaluminum whose concentration wasadjusted to 1 mmol/ml with 6.0 ml of toluene was slowly added dropwise.In that case, a gas was evolved. After stirring at 5° C. for 30 minutes,then at 80° C. for 2 hours, the supernatant was removed by filtrationand the residual solid compound was washed four times with 50 ml oftoluene. Then, 40 ml of toluene was added to form a slurry again, whichwas cooled to 5° C. in an ice bath, a mixed solution of 2.2 ml of atoluene solution of pentafluorophenol whose concentration was adjustedto 1.6 mmol/ml with 6 ml of toluene was slowly added. In that case, agas was evolved. After stirring at 5° C. for 30 minutes, then at 80° C.for 2 hours, the supernatant was removed by filtration and the residualsolid compound was washed four times with 50 ml of toluene and thenwashed twice with 50 ml of hexane. Thereafter, the solid compound wasdried under reduced pressure to obtain a flowable solid compound.

(2) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated, and hydrogen was added so that itspartial pressure became 10 mmHg, and 650 g of butane and 100 g ofbutene-1 were charged followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 0.5 ml of atoluene solution of bis (1,3-dimethylcyclopentadienyl) zirconiumdichloride whose concentration was adjusted to 2 μmol/ml was charged and30.6 mg of the solid compound obtained in the (2) described above wascharged as the solid catalyst component. The polymerization was carriedout at 70° C. for 60 minutes while feeding ethylene so that the totalpressured was held constant. As a result, 50.6 g of an olefin polymerwas obtained. The polymerization activity per transition metal atom was5.1×10⁷ g/mol Zr. hour and the polymerization activity per solidcatalyst component was 1650 g/g hour. The resulting olefin polymer hasSCB of 17.8, [η] of 2.03, Mw of 131000, Mn of 50000, Mw/Mn of 2.6, MFRof 0.26 g/10 min. and a density(without annealing) of 0.9082 g/cm³.

EXAMPLE 21

(1) Contact Treatment Between Particles(a) and OrganometallicCompound(b)

A 200 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 4.9 g of silica heat-treated at 800° C. (manufactured byDavison Co., Ltd., Sylopol 948; average diameter=54 μm; pore volume=1.66ml/g; specific surface area=312 m²/g; silica preserved under a nitrogenatmosphere after heat-treated at 800° C. by Davison Co., Ltd.) wascharged in the flask. Then, 200 ml of toluene was added to form aslurry, which was cooled to 5° C. in an ice bath, and 4.9 ml of atoluene solution of trimethylaluminum whose concentration was adjustedto 2 mmol/ml was slowly added dropwise. In that case, a gas was evolved.After stirring at 5° C. for 6 hours, the supernatant was removed byfiltration and the residual solid compound was washed four times with200 ml of toluene and then washed twice with 200 ml of hexane.Thereafter, the solid compound was dried under reduced pressure toobtain 5.3 g of a flowable solid compound.

(2) Compound(c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 2.6 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 50 ml of toluene was added to form a slurry, and 2.6 mlof a toluene solution of pentafluorophenol whose concentration wasadjusted to 2 mmol/ml was slowly added. In that case, a gas was evolved.After stirring at room temperature for 30 minutes, then at 80° C. for 2hours, the supernatant was removed by filtration and the residual solidcompound was washed four times with 50 ml of toluene and then washedtwice with 50 ml of hexane. Thereafter, the solid compound was driedunder reduced pressure to obtain 2.9 g of a flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated, and hydrogen was added so that itspartial pressure became 50 mmHg, and 735 g of butane and 15 g ofbutene-1 were charged followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 0.5 ml of atoluene solution of ethylenebis(indenyl)zirconium dichloride whoseconcentration was adjusted to 2 μmol/ml was charged and 35.1 mg of thesolid compound obtained in the (2) described above was charged as thesolid catalyst component. The polymerization was carried out at 70° C.for 60 minutes while feeding ethylene so that the total pressured isheld constant. As a result, 40 g of an olefin polymer was obtained. Thepolymerization activity per transition metal atom was 4.0×10⁷ g/mol Zr.hour and the polymerization activity per solid catalyst component was1140 g/g hour. The resulting olefin polymer has SCB of 18.5, a meltingpoint of 107.1° C., [η] of 2.50, Mw of 118000, Mn of 13000, Mw/Mn of8.9, MFR of 1.74 g/10 min. and a density(without annealing) of 0.9177g/cm³.

EXAMPLE 22

(1) Contact Treatment Between Particles(a) and OrganometallicCompound(b)

A 300 ml four neck flask equipped with a stirrer, a dropping funnel anda thermometer was dried under reduced pressure and then replaced withnitrogen. 27.8 g of silica heat-treated at ° C. (manufactured by DavisonCo., Ltd., Sylopol 948; average diameter=45.6 μm; pore volume=1.63 ml/g;specific surface area=527 m²/g; silica preserved under a nitrogenatmosphere after heat-treated at 300° C. by Davison Co., Ltd.) wascharged in the flask. Then, 170 ml of toluene was added to form aslurry, which was cooled to 5° C. in an ice bath, and 25.4 ml of atoluene solution of trimethylaluminum whose concentration was adjustedto 2.2 mmol/ml was slowly added dropwise. In that case, a gas wasevolved. After stirring at 5° C. for 30 minutes, then at 80° C. for 2hours, the supernatant was removed by filtration and the residual solidcompound was washed four times with 170 ml of toluene and then washedtwice with 170 ml of hexane. Thereafter, the solid compound was driedunder reduced pressure to obtain 29.6 g of a flowable solid compound.

(2) Compound (c) Treatment

A 100 ml four neck flask equipped with a stirrer and a thermometer wasdried under reduced pressure and then replaced with nitrogen. 1.76 g ofthe solid compound obtained in the (1) described above was charged inthe flask. Then, 50 ml of toluene was added to form a slurry, and 3.5 mlof a toluene solution of pentafluorophenol whose concentration wasadjusted to 1 mmol/ml was slowly added. In that case, a gas was evolved.After stirring at room temperature for 30 minutes, then at 80° C. for 2hours, the supernatant was removed by filtration and the residual solidcompound was washed four times with 50 ml of toluene and then washedtwice with 50 ml of hexane. Thereafter, the solid compound was driedunder reduced pressure to obtain 2.0 g of a flowable solid compound.

(3) Ethylene Polymerization

An autoclave (internal volume of 3 liter) equipped with a stirrer,wherein the atmosphere was dried under reduced pressure and thenreplaced with argon, was evacuated, and hydrogen was added so that itspartial pressure became 50 mmHg, and 735 g of butane and 15 g ofbutene-1 were charged, followed by heating to 70° C. Ethylene was addedso that its partial pressure became 6 kg/cm² and, after the system wasstabilized, 0.9 ml of a heptane solution of triisobutylaluminum whoseconcentration was adjusted to 1 mmol/ml was charged. Then, 0.5 ml of atoluene solution of ethylenebis(indenyl)zirconium dichloride whoseconcentration was adjusted to 2 μmol/ml was charged and 36.3 mg of thesolid compound obtained in the (2) described above was charged as thesolid catalyst component. The polymerization was carried out at 70° C.for 60 minutes while feeding ethylene so that the total pressured washeld constant. As a result, 120 g of an olefin polymer was obtained. Thepolymerization activity per transition metal atom was 1.2×10⁸ g/mol Zr.hour and polymerization activity per solid catalyst component was 3310g/g hour. The resulting olefin polymer has SCB of 21.1, a melting pointof 99.2° C. and 110.3° C., Mw of 84000, Mn of 26000, Mw/Mn of 3.2, MFRof 2.41 g/10 min. and a density(without annealing) of 0.9121 g/cm³.

INDUSTRIAL APPLICABILITY

According to the present invention, there is provided particles capableof giving a polymer having high activity and excellent shape andparticle properties when a catalyst for olefin polymerization obtainedby using a transition metal compound is applied to the polymerizationaccompanying formation of polymer particles (e.g. slurry polymerization,gas phase polymerization) by using in combination with the transitionmetal compound. Moreover, a carrier of said particles, a catalyst forolefin polymerization of said particles, a catalyst for olefinpolymerization using said particles, and a method for efficientlyproducing an olefin polymer having high molecular weight and narrowcomposition distribution using said catalyst for olefin polymerizationare provided.

Therefore, its utilization value is great.

What is claimed is:
 1. Modified particles obtained by a method whichcomprises contacting dry particles (a) with: (i) an organometalliccompound (b) that consists essentially of a compound represented by thefollowing general formula (1): R¹ _(n)AX_(q−n)  (1) wherein A representsa metal atom of the 2nd, 12th or 13th Group of the Periodic Table ofElements; R¹ represents a hydrocarbon group having 1 to 20 carbon atomsor a hydrocarbonoxy group having 1 to 20 carbon atoms and a plurality ofR¹ may be the same or different; X represents a halogen atom or ahydrogen atom and a plurality of X may be the same or different; nrepresents a number satisfying the expression 0<n≦q; and q is a valencenumber of the metal atom; and then (ii) a compound (c) having afunctional group containing an active hydrogen or a non-proton donativeLewis basic functional group, and an electron attractive group. 2.Modified particles according to claim 1, wherein the dry particles (a)are a porous substance.
 3. Modified particles according to claim 1 or 2,wherein the dry particles (a) are made of an inorganic substance ororganic polymer.
 4. Modified particles according to claim 1 or 2,wherein the dry particles (a) are made of an inorganic substanceheat-treated at 100 to 1500° C.
 5. Modified particles according to claim1, wherein the dried particles (a) are made of silica.
 6. Modifiedparticles according to claim 5, wherein the dry particles (a) are madeof silica heat-treated at 200 to 800° C.
 7. Modified particles accordingto claim 1, wherein the A is a boron atom, aluminum atom or magnesiumatom or zinc atom.
 8. Modified particles according to claim 1, whereinthe A is a boron atom or aluminum atom.
 9. Modified particles accordingto claim 1, wherein the A is an aluminum atom.
 10. Modified particlesaccording to claim 1, wherein the organometallic compound (b) istrialkylaluminum.
 11. Modified particles according to any claim 1,wherein the functional group containing an active hydrogen is a hydroxylgroup, mercapto group, amino group or phosphino group.
 12. Modifiedparticles according to claim 1, wherein the electron attractive group isa halogen atom.
 13. Modified particles according to claim 1, wherein thecompound (c) having a functional group containing an active hydrogen ora non-proton donative Lewis basic functional group, and an electronattractive group is a compound represented by the following generalformula (2): R² _(m)ZH_(z−m)  (2) wherein R² represents an electronattractive group or a group containing an electron attractive group; Zrepresents an atom of the 15th or 16th Group of the Periodic Table; Hrepresents a hydrogen atom; and z represents the valence of Z, or 2 or3, provided that: (i) m is 1 when z is 2, or (ii) m is 1 or 2 when z is3.
 14. Modified particles according to claim 13, wherein Z is a nitrogenatom, phosphorous atom, oxygen atom or sulfur atom.
 15. Modifiedparticles according to claim 14, wherein Z is a nitrogen atom or oxygenatom.
 16. Modified particles according to any one of claims 13 to 15,wherein R² is a halogenated alkyl group, halogenated aryl group,cyanated aryl group, nitrated aryl group or ester group.
 17. Modifiedparticles according to claim 13, wherein R² is a halogenated hydrocarbongroup.
 18. Modified particles according to claim 17, wherein R² is afluorinated alkyl group or fluorinated aryl group.
 19. Modifiedparticles according to claim 1, wherein a obtained treated particlesafter the contact are isolated.
 20. A carrier comprising the modifiedparticles of claim
 1. 21. A catalyst component for olefinpolymerization, comprising the modified particles of claim
 1. 22. Acatalyst for olefin polymerization, prepared by using the modifiedparticles (A) of claim 1 and a transition metal compound(B).
 23. Acatalyst for olefin polymerization, prepared by using the modifiedparticles (A) of claim 1, a transition metal compound(B) and anorganometallic compound(C).
 24. The catalyst for olefin polymerizationaccording to claim 20 or 23, wherein the transition metal compound (B)is a metallocene transition metal compound.
 25. The catalyst for olefinpolymerization according to claim 23, wherein the organometalliccompound(C) is an organoaluminum compound.
 26. The catalyst for olefinpolymerization according to claim 24, wherein the organometalliccompound (C) is a compound represented by the following general formula(4): R⁴ _(b)AlY_(3−b)  (4) wherein R⁴ represents a hydrocarbon grouphaving 1 to 8 carbon atoms; Al represents an aluminum atom; Y representsa hydrogen atom and/or a halogen atom; and b represents a numbersatisfying the expression 0<b≦3.
 27. A method for producing an olefinpolymer, which comprises polymerizing an olefin using the catalyst forolefin polymerization of claim
 22. 28. The method of producing an olefinpolymer according to claim 27, wherein the olefin is a mixture ofethylene and an α-olefin.